Causticizing of waste magnesia products



Jan. 11, 1944. H. F. vlEwEG ETAL i 2,338,885

CAUSTICIZING OFI WASTE MAGNESI PRODUCTS Filed Aug. 13, 1941 PC/P/TA TOR CA Us Tlc/2.572'v W45 7E INVENTORS Zen/m? (www/v6 TORNEY Patenteduan. 11, 1944 ICE cAUs'rIclzING or WASTE MAGNES VPRoDUo'rs ,l

Hermann F. Vieweg, Fort Sill, Okla., Arthur B. Cummins, Millington, N. J., and Thomas C. Pond, Larchmont, N. Y., assignors to Johns- Manvlle Corporation, New York, N. Y., acorporation of New York Application August 13, 1941, Serial No..406,584

4 Claims.

This invention relates to basic magnesium carbonate compositions of the type suitable for insulating purposes in the form of pipe coverings, blocks or the like, and particularly to magnesia products containing reclaimed magnesium.A ser Mm-1111s obtained from Waste magnesia ma' mais. The invention pertains especially to the novel procedure of treating waste magnesia materials in order to make the water-insoluble basic magnesium carbonates more susceptible to passing into solution upon treatment with ai In order to shape the crude molded products v,

of suchl basic magnesium carbonate compositions to accurate and proper sizes, it is necessary' to subject in many cases these molded farms to .sizing or finishing operations. As a result of the sizing or iinishing operations a considerable ouantityof the basic magnesium carbonate comyosition is lcst in the form of trimmings. These vtrimmings are usually in the form of dust andY small lumps. It has been estimated that approximately 20-60% of the weight of the nished products are accumulated as trimmings and waste material and the necessity of utilizing such large quantities of waste materials, including valuble magnesium compounds, in an economical manner will be readily apparent.

Another source of waste basic magnesium carbonate compositions, which may be utilized in the present invention, is made available in cases where existing insulated structures such a.. pipe ylines and boilers are stripped of old magnesia insulating materials. Materials thus obtained,y

have been previously discarded as waste, but through the applicationpof the procedure described in more detail below the magnesia components of these Waste materials can readily be recovered and used in manufacturing new insulating materials.

Efforts to reclaim waste basic magnesium carbonate compositions, in which we include dust, trimmings, broken blocks, broken pipe coverings and any other sources of waste products containing magnesia components, lhave previously been made. In the previous operations, waste'magnesla materials have been crushed and then Waste basic magnesium carbonate materials with added to fresh stock material but in following these procedures accumulated dirt and other undesirable nes were added and thus tended to increase the weight of, the final magnesia product. In another method designed to reclaim the insoluble basic magnesium carbonate materials, it has been proposedto convert the insoluble basic magnesium components into a soluble form of such compound by introducing carbon dioxide gas under high pressure and high concentration in an aqueous suspension of such waste materials. 'I'his method has, however, been found to be not entirely satisfactory and impractical due to the necessary high pressures and high concentrations of the carbon dioxide and the very limited conversion of the basic magnesium carbonate into the soluble magnesium bicarbonate.

Accordingly, itis an object of this invention tof convert the insoluble basic magnesium carbonate contained-in waste insulating materials into a magnesium compound which is more readily converted into the water-soluble magnesium compound without necessarily using high pressures and high concentrations of carbon,k dioxide gas. It is also an object'of this invention to treat waste vmagnesium compounds to convert the compounds into more readily Water-soluble compounds which will permit the use of higher temperatures in the carbonation step when cooling is not possible. Otherobjects and benefits of the present invention will be apparent to those skilled in the art from the more detailed description of the novel method described below.

Broadly stated', the invention includes treating magnesium compounds have been properlyv causticized, subsequent treatment with carbon dioxide gas at relatively low concentrations and pressure will readily convert the 'insoluble mag-` nesium hydroxide into water soluble magnesium bicarbonate compounds. Upon heating the magnesium bicarbonate solution, the magnesium compounds will precipitate as a self-setting normal carbonate or a basic magnesium carbonate,

depending upon the temperature and the length of time the solution is subjected to the heating operation. It will thus be clear that the reclaimed Waste basic magnesium carbonate matef rials may be utilized in preparing either self-setting normal magnesium carbonates or the conventional'baslc magnesium carbonates depending entirely upon the characteristics desiredin-the reclaimed magnesium compounds.`

'The invention willA be illustrated by amore complete ,description in -connection with the attached drawing which shows a iiow sheet of the method of manufacturing basic magnesium carr`bonate insulating materials in conjunction with t the preferred embodiment of the novel method employed inthe procedure of reclaiming waste basic magnesium carbonate compositions. i

In the drawing dolomite mineral preferably mixed with coke, is fed to a kiln and subjected to a calcination treatment. In the calcining 9peration the dolomite material is decomposed and carbon dioxide gas is driven from the calcium carbonate and the magnesium carbonate found in the dolomite mineral. The carbon dioxide gas obtained from the calcining operation may the precipitator. During the heating operation carbon dioxide -gas is driven from the magnesium bicarbonate `solution and the gas thus obtained may also be salvaged by usingit in the carbonation operation iny the saturator. 'I'he precipitated magnesium compounds are now passed to a weight are mixed with the precipitated materials conveniently be used in the carbcnator in a subi sequent step of the operation.

The calcined dolomite now containing primarily the mixture of calcium oxide and magnesium oxide is then passed into a slaking machine. In

the slaking operation water is mixed with the mixed oxides in order to begin the conversion of the oxides into the respective hydroxides, viz., calcium hydroxide and magnesium hydroxide. After the materials have been thoroughly wetted, a more complete hydration of the materials is made in the causticizer.

The causticizer is conveniently a relatively large tank in'which the materials are contacted by a large volume of water. It has been found that if the mixture is constantly agitated, more complete reaction of the materials will be obtained. -The calcium and magnesium components are now in the form of substantially waterinsoluble precipitates. that is, calcium hydroxide and magnesium hydroxide.

The mixed calcium and magnesium hydroxides are now pumped to a series of carbonating units. In the carbonator carbon dioxide gas is passed through the relatively thin slurry and the gas will react chemically with thesuspended calcium and magnesium hydroxides. The calcium hydroxide will be converted into substantially water-insoluble calcium carbonate and the magnesium hydroxide will be converted into the water-soluble magnesium bicarbonate compound. The concentration of the carbon dioxide gas can v carbonate. Similarly,

be relatively low, that is, the gas passing through the slurry may contain vabout 33% of carbon dioxide. low, that is, approximately lbs. per square inch gauge or lower. f-

After the mixture has been sufliciently carbonated, the magnesium bicarbonate'solution including the precipitated calcium carbonate is Dumped into a thickening tank. In the thickening tank the calcium carbonate is allowed to settle to the bottom of the container and the substantially clear magnesium bicarbonate solution is then pumped into a precipitator. The settled calcium carbonate material frequently referred to as waste or lime sludge is removed from the thickener. This sludge contains a considerable quantity of precipitated magnesium carbonate and also a considerable proportion of magnesium bicarbonate solution retained or abmrbed by the sludge particles.A These magnesium compounds are recovered by a method which is more fully described and claimed in the copending application of Thomas F. Atchison, Serial No. 406,577.

The substantially clear magnesium bicarbonate solution is then subjected to a heating action in Also, the pressiire can be kept relatively and after a thorough 'mixing the mixture is transferred. into molds in the form ogblocks, pipe covering, or any ,other shape which might be desired in the final product. After the molded materials have been formed, the materials are subjected to a drying operation to remove substantially all the Water from the material.

' The shaped and dried basic magnesium car# bonate materials obtained as described above, are

now subjected to a trimming operation.v The trimming operation is essential in order to shape and cut the molded magnesia product to the proper dimensions. These trimmings are oit times referred-to in ,the industry as plastic, and a proportion of these trimmings have heretofore been re-used in the operations by merely grinding the trim to a relatively small mesh and then mixing the pulverulent material with fresh ingredients. l

The accumulated trim in the p'resent operation is preferably ground to a particle size of about 20-60 mesh and then placed into the causticizer Atively large particles and rthen pass the trim over ordinary separating screens to remove the asbestos fibres from the crushed trim before passing the material into thecausticizer. Y' The magnesium compoundsin the plastic trim are substantially in the form of. basic magnesium the magnesium com-l pounds in wastejmagnesia products referred to above, are also in the iorm of basic magnesium" carbonate.

In the causticizer the basic magnesium-carbonate will react with calcium hydroxide usually derived from the calcined hydrated dolomite to form a substantially water-insoluble magnesium hydroxide.' If, however, dolomite materials are l not used as raw materials in the magnesla prod- -uct manufacturing process, lime or caustic soda may be added to the basic magnesium carbonate in order to obtain the necessary causticizing reaction. ,.The lime will react with thebasic magnesium carbonate to i'orm a substantially waterinsoluble magnesium hydroxide. The reaction proceeds forward in the same manner as the reaction between the basic magnesium carbonate and the/calcined dolomite.

It is well recognized that basic magnesium carbonate will react relatively slowly with carbon dioxide gas in the conversion of the basic magnesium carbonate into the water-soluble magnesium bicarbonate. If, however, the basic magnesium carbonate is treated with an alkaline earth hydroxide, such as calcium hydroxide, as described above, prior to the carbonation step. the thus-formed magnesium' hydroxide is more pitated magnesium com- A asasee 3 readily convertible into the water-soluble magmaterials and L61.7% `from calcined hydrated nesium bicarbonate. The solubility of-the two dolomite, is carbonated after approximately 2 compounds will be illustrated by consideration of hours of causticizing treatment, that practically the following experimental data on the carbona'- all the magnesium compounds from both sources tion of trim materials: K 5 ,are taken into solution. The data further shows that the ultimate concentrations of magnesium bircarbonate corresponding to 1.73% basic magnesium carbonate as compared to onlyf.95% ofv magnesium being takerr-nto solution from or- SOLUBILITY or' BAsIc MAGIIESIUM CARBoNAr's (PLAsrIc TRIM FROM MAGNEsIA INsULA'IIoNs) BY CARBON DIoxInE (7 Ln. GAUGE PRESSURE CO2) Table I ,l l0 dinary uncaustiized basic magnesiumcarbon'- f ate. The conditions of temperature and carbon concentrati@ dioxide pressure were vthe same in each case, Ofmfgneslm Table I showing the concentration cf magnesia i solution as the Temperature, F. l bicarbonate in solution 1n the form of a bicarbonate expressed l (@xllfessed as 15- as equivalent of basic magnesium carbonate and equivalent of @basic megnesimn Table III shows the concentration of -iriagnesia l carbonate) taken into solution as the bicarbonate expressed as equivalent of`basic magnesium carbonate after i causticization treatment.

sium compounds be subjected to suflicient causticizing action in order to obtain the desired SoLUBILIrY or MAoNrisIUM HYDRA'I'I: (FROM SLAKED and ecient results. If the magnesium com- DoLoMITE) 1N CARBON DIoxIDE (7 LB. GAUGE pounds are incompletely causticized, the recov- PREssURn CO2) 25 ery of the magnesium compounds will be incom- -Tlbl6 Il plete. This ris evidenced by consideration of the data in the following tables:

Concentration oflmtqgnesiatrin Table IV souionaS c 01dluiiteu'ln Temperature FI "bicarbonate [Carbonation of mixes containing 40% plastic 60,0 o o g u (expressed as 7 lbs. gauge CO1] b equivalent of BSIC magnesium carbonate) '(101, (b)

poi'omiteused i.o5'7 1.207. Pg' M 35 Plastic used (x700/2..--. c800/,l 2-36 i Total Mgavaiiap i 75% 2.00%. 1'79 Causticization tim 15 minv 1%l1r.

It will be evident from the data that a considerably higher proportion of magnesium com- 40 'rime of carbonation Contiggtm Contgtr" -pounds will pass into solution in the form of magnesium bicarbonate by converting 4the basic 15 in ner cent 0.90' L20 magnesium carbonate into the magnesium hy- 30111111.11 fio.. 1.42 1./ 80

drate before treatingA with carbon dioxide gas. n'l" *ggj jg, jg The eiect of treating Waste basic magnesium 75 min..- dgF 1.50 2.00

carbonate materials with a'causticizing mate- Fmaltempemt f 79 75 rial is also illustrated by consideration of the following additional data which sh'ows the high recovery of the magnesium `components .as a

Furtheri'data on the time of causticizing using 25 1b. gauge pressure CO2 are set forth in,

e Table V.

o f' result of the novel treatment. .i0 Table V CARBoNA'rIoN or PLASTIC BY CAUsrIcIzfING [Eect ofcausticzng tme 251bs. C01] METHOD (ADDITION oF PLAsI-Ic MAGNESIUM CAR- v i BoNA'rE. TRIM To HiInRA'rE CALCINED DOLOMITI-i s (a) (d) PRIOR ro SATURATION) V oo Dolomiteused... 1.057... 10m/ 1.05%.. 1.057. me tra Hai-- iai"- sa? i ata ava a e.-. [Temperatura 100 F.,7lb.gaugepressurc C02] Causticizng time n 10 o 40 o n 1hr-o"- 65mg Concentration of magnesia in ,f solution as the bicarbonate (expressed as equivalent of i D l t Sed basijnagnesium rbong) 60 l v C C, C y C- 0 01111 e 11 I: .I 0110811- ODCBII- IODCGD- Olllllli Plastic used 0.677o Tune of carbonation tration tration tration tration Total available.. 1.75 o Caustieizing time 2 hrs. 20 min.

. 1.47 1.6 1.69 C i' tt H 0110821- X Time of carbonation y l tration 1 62 85 a5 75 Pcrce'nt 0.03 i 3 Tables IV and V leilnitelij show that the length 1167 of time to which the materials -are subjected to L73 the causticizing treatment should be sufficiently 'L long so thatgthe conversion from the basic mag- The data compiled in Table III shows that when nesium carbonate to the water-'.,insoluble maga mixture, the total magnesia of which comes vnesiu'nrhydroxiiie will be substantially complete.

38.3% from waste basic magnesium carbonate 75 A period of time approximately '45 minato I 20 It is important that the waste basic magne-- hour is considered adequate to permit substantially complete conversion oi.' the basic magnesium carbonate in a mixture containing 40% waste basic magnesium carbonate materials and l 60% calcined hydrated dolomitel for. satisfactory carbonation of the materials in order, to obtain complete recovery in the form of magnesium bicarbonate. If the percentage of waste basic magnesium carbonate compound is increased, as, for example, 55% ofwaste .basicl magnesium carbonate materials and 45%' of calcined hydrated dolomite, it may be necessary to increase the causticizing time. If the pressure of the carbon dioxide gas is increased from 'I pounds gauge pressure, Table IV, to 25 pounds facturing shaped magnesia insulationproducts, wherein magnesium bicarbonate solution is concerted to basic magnesium carbonate, which, in

ture with asbestos fibres, is molded and the olded mixture cried and trimmed to dimensions, hich comprises, forming a dilute aqueous' s pension of the waste products of said trimming operation and calcium hydroxide and agitating said suspension to convert the basic carbonate to magnesium hydroxide, subjecting the .resulting suspension to carbonation with carbon gauge pressure, Table V, the time required for l the causticizing treatment may be decreased.

Infollowing the procedure described, waste basic magnesium carbonate materials are eiectively recovered and utilized in new mmesia products. 'I'he causticizing treatment prior to dioxide at substantially normal temperature and under 'a pressure inthe range 7-25 lbs. gauge to conyert the magnesium hydroxide to magnesium bicarbonate, and adding' the magnesium bicarbonate thus formed to the original bicarbonate solution for reconversion to basic magnesium carbonate. y i

v3. The method of treating basic magnesium carbonate waste material produced during the Imanufacture of magnesia heat insulation prodthe carbonation of the waste magnesia products` within the scope of the invention as defined by' the subjoined claims.

We claim: l

1,'A cyclic process of manufacturing shaped magnesia insulation products which comprises, calclning dolomite and hydrating the calcined dolomite to produce a dilute, aqueous suspension of calcium and magnesium hydoxides, carbonat- K ing said suspension to form asolution of magnesium -fbicarbonate and precipitated insoluble calcium carbonate, separating the precipitate and heating the bicarbonate solution to' precipitate basic magnesium carbonate, molding the basic carbonate and drying and trimming the molded shapes to dimensions, causticizing the waste material produced by said trimming operation by adding it to said suspension of calcium and magnesium hydroxides, and agitating the mixture to convert the magnesia trimmings to magnesium hydroxide.

2. That improvement on4 the process ofmanuucts which comprises, causticizing said material 'by adding it to a dilute aqueous suspension of calcined hydrated dolomite, extending said causticizing operation with agitation over a period sumcient to-'efrect conversion of the magnesia values to the form of magnesium hydroxide, carbonating the resultinglsuspension with carbon dioxide at 'substantially normal temperatures and under comparatively low pressure below 45 lbs. per square inch gauge to convert the magnesia lvalues to soluble magnesium bicarbonate, and

separating the resulting magnesium bicarbonate solution from insoluble calcium carbonate simul.

taneously formed.

4. The method of treating` trimming wastes resulting from the manufacture of basic magnesium carbonate heat insulation products which comprises, reducing Jsaid trimmings to a fineness of 20-.60-mesh and separating asbestos fibres associated therewith, adding the resulting basic carbonate nes to a dilute aqueous suspension of calcined hydrated dolomite and caustieizing a minor proportion by weightof the basic carbonate with an excess of the calcined hydrated dolomite to con.- vertthe magnesia values to magnesium hydroxide, carbonating the resulting suspension with carbon dioxide at substantially normal temperature and under a relatively low pressre in the range 7-25 lbs. gauge, and separating the aqueous solution -of magnesium bicarbonate thus formed from insoluble calcium carbonate HERMANN F. VIVEWEG. ARTHUR B. CUMMINS. `THOMAS C. POND.

Certificate of Correction Patent No. 2,338,886. January 11, 1944. HERMANN F. kVIEWEG ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 3, first column, line 52, heading to Table III, for the Word PLASTIC read BASIC; line 53, for HYDRATE read HYDRATED; and second column, line 9, for magnesium read magnesia; and that the said Letters Patent should be read with these corrections therein that the Same may conform to the record of the case inthe Patent Office.

Signed and sealed this 25th day of April, A. D. 1944.

[SEAL] LESLIE FRAZER,

Acting Commissioner of Patents. 

